Aspects of the chemistry of enol ethers : synthesis and reactions
Aspects of the chemistry of enol ethers : synthesis and reactions
The isolation and structural assignment of gloeosporone and pseudo-gloeosporone are described. Total syntheses of /weiuio-gloeosporone from the laboratories of Schreiber and of Holmes are discussed. A review of methods for the synthesis of the oxocane ring system is presented.
Our total synthesis of preiuio-gloeosporone is described. Key steps are: the intramolecular directed aldol condensation to construct the oxocane ring; and the photo- oxidation of a silylfuran to construct the f-keto acid moiety.
A historical review of alkene bond forming reactions of metal- carbene complexes of Group IV metals is presented. The scope of the stereose-lective alkylidenation of ester cabonyl groups by a reagent prepared from a 1,1-dibromoalkane, zinc, T1CI4, and TMEDA in THF for the synthesis of (Z)-enol ethers (the Takai reaction) is explored and extended to include acid- sensitive alkoxy and terminal alkene functionality. Such enol ethers are further elaborated to a series of spiroacetals.
The general and mild nature of the Takai reaction is placed into context with regard to other literature procedures for the synthesis of trisubstituted (Z)-enol ethers. The scope of the reaction is enlarged to include branching in both ester and 1,1-dibromoalkane partners and to further use of acid-sensitive substrates. The effect of temperature on the reaction is examined. A proposed mechanism for the reaction is discussed. The synthesis of the 1,1-dibromoalkane compounds is described, as too are attempts at novel routes to such moieties. (DX84440)
University of Southampton
1988
Mortimore, Michael Paul
(1988)
Aspects of the chemistry of enol ethers : synthesis and reactions.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
The isolation and structural assignment of gloeosporone and pseudo-gloeosporone are described. Total syntheses of /weiuio-gloeosporone from the laboratories of Schreiber and of Holmes are discussed. A review of methods for the synthesis of the oxocane ring system is presented.
Our total synthesis of preiuio-gloeosporone is described. Key steps are: the intramolecular directed aldol condensation to construct the oxocane ring; and the photo- oxidation of a silylfuran to construct the f-keto acid moiety.
A historical review of alkene bond forming reactions of metal- carbene complexes of Group IV metals is presented. The scope of the stereose-lective alkylidenation of ester cabonyl groups by a reagent prepared from a 1,1-dibromoalkane, zinc, T1CI4, and TMEDA in THF for the synthesis of (Z)-enol ethers (the Takai reaction) is explored and extended to include acid- sensitive alkoxy and terminal alkene functionality. Such enol ethers are further elaborated to a series of spiroacetals.
The general and mild nature of the Takai reaction is placed into context with regard to other literature procedures for the synthesis of trisubstituted (Z)-enol ethers. The scope of the reaction is enlarged to include branching in both ester and 1,1-dibromoalkane partners and to further use of acid-sensitive substrates. The effect of temperature on the reaction is examined. A proposed mechanism for the reaction is discussed. The synthesis of the 1,1-dibromoalkane compounds is described, as too are attempts at novel routes to such moieties. (DX84440)
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Published date: 1988
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Local EPrints ID: 460844
URI: http://eprints.soton.ac.uk/id/eprint/460844
PURE UUID: ed19fefd-6e93-4410-aad8-f694b5f9a492
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Date deposited: 04 Jul 2022 18:30
Last modified: 04 Jul 2022 18:30
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Author:
Michael Paul Mortimore
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